Fluorohydrocarbon substituted silanols



Patented May 26, 1953 FLUOROHYDROCARBON SUBSTITUTED SILANOLS Charles F. Kohl, Jr., Pittsburgh, Pa., assignor to Corning Glass Works, Corning N. Y., a corporation of New York No Drawing. Application October 27, 1949, Serial No. 123,991

1 Claim. 1

The present invention relatesvto a new class of organosilanes and to methods for their preparation.

In general, in the organosilicon art the organic radicals which are linked to silicon are monovalent hydrocarbon radicals. U. S. Patent 2,258,219 describes the preparation of chlorophenylsilicon chlorides and. fluorophenylsilicon chlorides. The hydrolyzates of these silanes are readily condensable similarly to silanes which do not contain halogen substituents in the organic radicals.

Objects of the present invention are to provide methods for the preparation of silanes, the hydrolyzates of which are relatively quite stable in comparison to the heretofore known organosilanols.

The silanols in accordance herewith are of the general formula:

[ -1 suon) (4-...)

where n is a positive integer less than 3 and m is a positive integer less than 4. When the silanols are prepared from the corresponding fluoromethylphenylchlorosilanes in relatively pure form, the value of m is a whole number. When mixtures of chlorides are employed in which chlorides there are present silicon chlorides having varying numbers of the fluoromethylphenyl radicals, m then has a positive value of from 1 to 3. These products do not represent copolymers, but merely mixtures of various silanols.

The silanols hereof may be prepared by hydrolysis of the corresponding chlorides which contain chlorine bonded to silicon in place of the hydroxyls. These chlorides may be prepared by reacting silicon tetrachloride with a trifluoromethyl substituted bromobenzene Grignard reagent. The Grignard reagent is prepared by reacting magnesium with said bromobenzenes. The Grignard reagent so produced is reacted with the silicon tetrachloride at below 80 C., whereby at least one trifluoromethyl substituted phenylradical is bonded to the silicon of the silicon chloride. The coupling of the Grignard reagent with the silicon chloride is effected at a temperature below80C.

The preparation of .fiuoromethyl substituted phenyl bromide by the bromination of trifiuoromethylbenzenes has been described by tsimons and Ramler in 1943 inthe Journal of the Amer} ican Chemical Society, volume 65, page 389l ln accordance with this method thebromination is effected in liquid phase at 0. They indicated that the compounds obtained were exclusively those in which the bromine was in meta position. Bromination of these compounds can also be obtained by passing a mixture of the fluoro hydrocarbon and bromine in vapor phase through a reactor :at a temperature in the range of 700 to 900 'C. By this method the ortho compounds can be obtained as well as the meta compounds, together with small amounts of the para derivative.

One suitable compound for the preparation of the bromide is trifluoromethylbenzene. Other bromides may be prepared from the bis (trifluoromethyhbenzenes such as the compounds of this type in which the two trifluoromethyl radicals are in the 1,3 and 1,4 positions.

The Grignard reagents are produced by reacting the bromides as above described with magnesium. It should be noted that great care should be employed in the preparation and handling of these Grignard reagents inasmuch as violent explosions may occur, particularly if the temperature limit herein stated is exceeded. In the reaction of these bromides with the magnesium, the temperature should be held below C. It is also of assistance in preventing detonation of these materials to operate in the presence of a solvent such as ether, or a low boiling hydrocarbon. The chlorine analogues of the above bromides do not appear to formGrignard reagents under the conditions stated.

The Grignard reagents so produced are then reacted with silicon-tetrachloride. The silicontetrachloride is mixed with the Grignard reagent and maintained at below 80 C. The coupling reaction proceeds with relative ease.

In making the coupling, the silicon tetrachloride is employed in amount at least equivalent to the amount of Grignard reagent employed. Preferably less than ten equivalents of the silicon tetrachloride are present per equivalent of Grignard reagent.

The products of the coupling reaction are of the type:

' SiCl (M) (C F a) m customary with silanols. Some condensation can be effected with materials in which there is but one trifluoromethyl group on the phenyl radical. It has been impossible, however, to effect polymerization of the condensed material by methods generally applicable for the polymerization of siloxanes.v When two trifiuoromethyl groups are linked to. the phenyl radicals, the silanols are non-condensable except that a slight condensation can be effected with the hydrolyzate of bis.- (trifiuoromethyDphenyl trichlorosilane. It has been found that the products of hydrolysis areuseful for such purposes as interacting with polydimethylsiloxanes whereby the siloxane. is; stabilized and for the preparation of copolymers with. other siloxane units. The present invention is a continuation-in-part of my application, Serial No. 786,541, filed November 17, 1947'.

The following examples illustrate the present invention Example 1 B. P., o 0. o

(1); F'lCQtH4 lC1a 108 at 47.4 mm N 4678 (2) (FaCCsH'flzSiClz. 124.7 at 3.4 mm 1. 4274 1 4884 (3) (F3CC6H4)3S1C1 o 154.2 at 0.7 min 501,8.

Each of these compounds was hydrolyzed and the respective silanols were thereby obtained. Compound (1) was hydrolyzed by pouring it into water which contained an excess of sodium hydroxide. The trial so formed was soluble in the aqueous phase. This was precipitated by acidification of the residual alkali. Some slight condensation had occurred at this point. Further condensation can be effected by heating at 150 C. A solid resin is obtained which it is impossible to condense to the point that it becomes insoluble in hydrocarbon solvents. Compound (2.) was similarly hydrolyzed and the. crystalline diol was obtained. This may be copolymerized with dimethylsiloxane. When the diol is condensed alone, very thermally stable fluids are obtained which are only slightly volatile. Thus, this fluid has been employed as a coating over molten lead to prevent oxidation. While there was some loss. of the fluid due to vaporization at this high temperature, the residual silcxane was still a mobile fluid after one thousand hours exposure to air under these conditions. Compound (3) upon hydrolysis produced a silanol of exceptional Stability. Compound (1) was converted to the trifluoroe methylphenylsilicon triflucride by reacting the chloride with antimony trifiuoride. When this compound was hydrolyzed by the method described in connection with the chloride a stable oil was produced. Compound (1) was heated for one hour with fuming sulphuric acid. This resulted in the removal of only 20 per cent of the trifluoromethyl radicals, whereas this treatment removes all the phenyl radicals from phenyltrichlorosilane.

By reducing the amount of SiCh with which the Grignard reagent was reacted to 1.5 equiv 4 alents of SiCh per equivalent of the Grignard reagent, the ratios of compounds (2) and (3) to compound (1) were increased. Compounds (2) and (3) were cohydrolyzed by refluxing a mixture thereof with an excess of 5 per cent aqua ammonia. The hydrolyzate condensed to, give a product. of the formula RJSiQSiRZOSiRB, where R represents F3CCeH4. This is a very stable material boiling at 240 C. at 1 mm., and at about 550 C. at atmospheric pressure. This is, accordingly, an excellent material for an indirect heat exchange medium for operation either at its boiling point or therebebow. It has a density of 1.4084 at. 26 C1. and an index of refraction of 1.4948 at 25C.

. Example 2 These bromidesv are readily separable by distillation.

The Grignards of each of compounds (4') and. (5) were prepared by the method described in Example 1, following which the Grignard reagents were reacted with silicon tetrachloride. From the reaction involving compound l) the following products were obtained:

B.P.,C. I D30 (5), 5, bis 1,3 (trifluoramethyl) phcnyltrichlorosilane.

(7) bis 5,5 [bis 1,3 (trifluoromcthyl) phcuyl] dichlorosilane.

(8) tris 5,5,5 [bis 1,3 (trifiuoromcthyl) phenyl] chlorosilane.

5.5-5.1.2 at 1.7 mm 1. 532

116.6 at 214 mm 1. 567 1. 4424 156 at 1.8-2.3 mm l. 552 1. 4445 Compound (6) is a low viscosity fluid. Compounds (7) and (8) are low viscosity fluids which crystallize on standing. Compounds (6)., (7) and (8) were hydrolyzed by the method described in Example 1. The hydrolyzate of compound (7) when heated condensed somewhat to produce a viscous fluid which had little flow at room temperature. The hydrolyzates of compounds ("7) and (8),. were relatively pure silanols. The silane diol from hydrolyzing compound (7) melted at 220. C. Thev melting point of this compound remained constant upon recrystallization. The silanol from compound (8) melts at an even higher temperature without condensing to the siloxane. This silanol is so stable that, when melted with toluene chlorosulfonic acid, the latter vaporizes from the molten mixture without in any way affecting the properties of the silanol.

Similarly the Grignard was prepared of com pound 5) and reacted with an excess of silicon I tetrachloride. The following silanes were produced:

(9)6 bis 1,4 (trifluoromethyl) ca.80 at25mm (15))h%nyl grchlgrosilane. t n

g is is ,4 (riuorolQ9.5 ll( 1at 3n1m (linehyl a g enlygl dlic4hl(oroailane. l 4248 ns is tri uorol to,l60at3mm. 1.. methyl) phenyllchlorosilane.

Compound (9) was similar to compound (6) in its physical and chemical properties. Compound 10) was a high viscosity fluid as contrasted with compound (7) which was of low viscosity. Furthermore, compound (10) did not crystallize on standing. Upon hydrolysis as above described the hydrolyzate was non-crystalline. Compound (11) was so viscous that it had virtually no flow at room temperature nor did it crystallize.

The hydrolyzates of compounds (6) to (11) may be added to polymeric dimethylsiloxanes. Upon heating in the presence of air, the mixture gradually thickens though at a much lower rate than the polymeric dimethylsiloxane to which none of these hydrolyzates have been added. After heating to the point that it gels, the gel so produced is characterized by its extreme toughness particularly as contrasted to the gel produced from the polymeric dimethyl silicone alone, which latter gel is crumbly.

Analytical data in connection with the above compounds are not here given inasmuch as both the chlorides and the silanols are so stable and refractory even in the presence of fuming nitric and fuming sulphuric acids that they do not lend themselves readily to customary analytical methods. This, however, illustrates the outstanding stability of these materials.

That which is claimed is:

where n is a positive integer less than 3 and m has a positive value of from 2 to 3.

CHARLES F. KOHL, JR.

No references cited. 

